SPE Library
The SPE Library contains thousands of papers, presentations, journal briefs and recorded webinars from the best minds in the Plastics Industry. Spanning almost two decades, this collection of published research and development work in polymer science and plastics technology is a wealth of knowledge and information for anyone involved in plastics.
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Conference Proceedings
Quantitative Determination of Interfacial Strength in Commercial Coatings and Laminates
Hung-jue Sue, February 2020
Delamination in coatings and multilayered polymeric sheets and films, which compromises the mechanical integrity and intended functionalities, are commonly found in commercial products. Known acceptable approaches, such as the double-cantilever-beam test, for quantifying adhesive strength in commercial coating and laminated products are difficult to implement. The practical ASTM D3359 and ISO 2409 crosshatch-cut and tape-pull standards are too crude and gives inconsistent results. In this presentation, two new test methodologies have been developed for quantitative determination of interfacial adhesion in coatings, semi-rigid sheets, and soft multi-layer polymeric films. These new test methods involve the utilization of a highly instrumented machine to perform the tests, followed by finite element methods modeling to obtain the associated stress magnitude for determining the interfacial strength in coatings, semi-rigid laminates, and soft multilayer films. Consequently, fundamental structure-property relationship can be established based on commercial products. Examples of success based on a few commercial coatings and polymeric laminates will be presented.
A 30 Year Retrospective of BASF Antioxidants for Polyolefins; 1990-2020
Rick King, February 2020
By the end of the 1980s, the combination of phenolic antioxidants and phosphite based melt processing stabilizers had been firmly established as the traditional cornerstones of a representative stabilization system for polyolefins. Even so, there was still room for improvement. Accordingly, over the next thirty years, an enormous amount of work was done to continue developing new stabilizer chemistries, and to further advance the frontiers of polymer stabilization. An overview of selected products will be provided, along with examples of how some of these products became unique solutions to help polyolefins continue advancing as the preferred material of choice in the plastics industry. Most recently, we have been exploring novel approaches to use our BASF Antioxidant technology platform to further enable the goals of “Reduce, Reuse, Repurpose and Recycle."
Effects of Molecular Weight of Thermoplastic Fluorinated PPA on Various Melt Index LLDPE Polymers
David Seiler Sr., February 2020
The paper will study the performance for a series of fluorinated thermoplastic polymer process aids (PPA) in different LLDPE polymers with varying melt index from fractional melt to 3.6 dg/minute. The study compares results for fluorinated thermoplastic PPAs of different molecular structure in LLDPE and will help in the understanding of how the variation of LLDPE Melt Index (MI) can lead to selection of the preferred PPA for optimum processing. The study utilizes a flat-die extrusion testing method to evaluate key performance results such as speed of melt fracture elimination, speed and amount of pressure reduction, other observations, and how these performance enhancements vary depending on the MI of the LLDPE.
The Next Generation of Non-Alkylphenyl Polymeric Phosphites: Increased Phosphorus and Performance
Michael Jakupca, February 2020
Phosphites are widely used to improve the thermal stability of polymers during melt processing. The performance of a phosphite is related to the percent of phosphorus in the molecule, higher levels of phosphorus result in increased melt flow stability. Dover Chemical has previously introduced a polymeric phosphite that has many benefits, such as good process stability, excellent color retention during melt processing and aging, low migration, no compatibility or plate-out issues and unique melt fracture synergy with polymeric process aids. A new polymeric phosphite will be introduced in this paper, that has the same beneficial properties, but with a 50% higher phosphorus level. This presentation will examine the performance of this second generation high performance liquid polymeric phosphite.
Plastic Additives, Fit for Use in Sensitive Applications, Safe Pure Transparent
Tracey Malone, February 2020
Plastic Additives can be used in sensitive applications such as food contact and/or water pipes. Supplying these products into the global marketplace requires that standards and practices must be established that can assure the products are of a purity suitable for the intended use. Global regulations supply the requirements for assessing the safety of non-intentionally added substances (NIAS). Since many plastic additives undergo chemical transformations as they perform their functions during plastic fabrication and use, identification and evaluation of these substances and Good Manufacturing Practice requirements for plastic additives during synthesis and blending have become more explicit. NIAS that originate from various sources must be assessed and controlled. We will share BASF’s programs to identify and mitigate risks in this area to ensure safe products and our commitment to responsible care.
Creating High-Value Added Glass Fiber Reinforced Polypropylene via Polymer Additives Technology
Yota Tsuneizumi, February 2020
Utilization of plastics is expanding in the course of the development of compounding and additivation technologies for a light weight solution in automotive, insulative and advanced design in E&E application. Among plastics, polyolefin in particular, polypropylene is one of the key materials from the standpoint of well-balanced physical/mechanical properties and cost. Glass-reinforced polypropylene (GFPP) and Talc-filled PP are already being used in these application to replace engineering plastics and metals. These compounds are used in structural components that require high levels of stiffness, strength and heat resistance, predominantly within automotive, appliance and furniture applications. However, it is well known that polyolefins degrade rapidly by auto-oxidation reaction under extreme conditions. There are also disadvantages to polypropylene by filling glass fiber, such as increase of brittleness and decrease in flowability. In this paper, the contribution of the additives in GFPP is explained. Against the severe processing temperature of GFPP, a combination of antioxidants showed remarkable stability. Nucleating agents can improve the mechanical properties, resulting in weight reduction of the polypropylene composites and the reduction of cycle time. By the use of specific NA, data suggests that the amount glass fiber could be reduced while maintaining the compound’s mechanical properties, which will contribute to weight reduction. Additionally, the flame retardancy which could be achieved by an intumescent type flame retardant (FR) in GFPP will also be discussed.
Interactions Between Sorbitol Nucleator and Other Common Additives in Polypropylene
Olivier Nguon, February 2020
Polypropylene (PP) is one of the most produced thermoplastic polymers, offering excellent physical properties, good processability, and low cost. The performance of this material is contingent on its semicrystalline structure. One common method to enhance the crystallization rate is the addition of nucleating agents. Sorbitol compounds, in particular, have proved effective, at low concentrations, at improving both mechanical and optical properties while shortening processing times. Other additives have widespread use to facilitate processing and prevent polymer degradation. For instance, fatty acids and antioxidants are frequently compounded with PP. However, the interactions between the different additives are generally unknown, and may yield antagonistic interactions, nucleator deactivation, and inferior properties. We studied the synergistic and antagonistic interactions between 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol (TBPMN) and four additives (processing aids and antioxidants). We showed improved crystallization temperature (Tc) in presence of the antioxidants, while calcium stearate was found to inhibit nucleator activity. The performance of TBPMN in presence of mono-glycerides was found to highly depend on the processing conditions. From 1H NMR, and FTIR analysis, we posit that hydrogen bonding and/or oxidation of the nucleator took place with these additives, and inhibited the network formation in the polymer matrix. The method of addition of nucleators and other additives to polypropylenes is an important parameter to achieving the best performance in the final product.
Beyond Antioxidants: Using Microcompounding to Evaluate Stabilizer-Systems in Polypropylene
Niall Marshall, February 2020
It has been shown that studying the processing stability of polypropylene using continuous micro-compounding provides comparable results with statistical repeatability to the traditional multiple extrusion approach but with the added advantage of being quicker and requiring less material. Using this approach we have further compared the performance of different stabilizer systems made up of primary- and secondary-antioxidants at different loadings to evaluate the efficacy of stabilizer systems rather than of the various antioxidants themselves.
Talc as Antiblocking in LLDPE: Evaluation of Performance in LLDPE Films of Talc Versus Other Mineral
Ercoli Malacari Piergiovanni, February 2020
As many plastic films tend to stick together, making difficult to separate film layers, some mineral additives are used to improve this situation. Specifically, in LLDPE films micronized talc is often used as antiblocking agent. Thanks to the micro-roughness achievable on film surface, talc acts as a spacer between the film layers minimally affecting transparency and other mechanical properties. The presence of talc in the LLDPE film formulation interacts with other additives, creating a unique set of properties that makes talc a very effective additive for film applications. In this paper, talc will be investigated for its intrinsic characteristics in comparison with other known mineral antiblocking additives to evaluate their effect in LLDPE film. A comprehensive evaluation of several properties will be performed to rank each single tested additive for the antiblocking function, considering all the side properties including mineral additive abrasivity and bulk handling It will be also introduced a novel talc antiblocking additive characterized by free-flowing appearance and dust-free behavior, for innovative solutions in talc handling.
Enhanced Stabilization System for Polyolefin Water Pipes
Jungdu Kim, February 2020
Polyolefin materials by itself are not suitable for long-term applications due to their too high sensitivity to oxidation. The major technology step to slow down the oxidation of polyolefins in the solid state are sterically hindered phenols (often referred to as phenolic antioxidants). This principle technology, developed already in the 1970s, enables service lifetimes of polyethylene thick section articles (e.g. pipes) in excess of 50 years. This technology had later-on to be finetune for (drinking) water pipes to avoid the extraction of the phenolic antioxidant during the contact with water and to ensure service life in the presence of free chlorine in drinking water. Particularly polypropylene-random copolymers (PP-R) has been a material of choice for use in the production of plastic pipes for hot and cold water for more than 20 years. Long-term thermal stabilization (LTTS) was traditionally based on phenolic antioxidants and thioesters. The thioester was later dropped, as it had a negative effect on the taste and odor of the water. Nowadays, single phenolic antioxidants or combination thereof are the key components for LTTS. In the drinking water system chlorine dioxide (ClO2) prevents the formation of germ or bacteria, however it is much more aggressive than hypochlorous acid and chloramine and leads to premature failure of polyethylene pipes. The paper presents solutions to significantly to extend service life of PP-R in water extractive applications and improve the stabilization of polyethylene pipes in contact with water containing ClO2.
Analytical Technology to Meet the Challenges of a Sustainable Plastics Economy
Robert Bruell, February 2020
Additives are widely used to tailor polymer properties like clarity and mechanics, and long-term characteristics like durability for particular applications. Due to the constant emerging of new additives a continuous development of appropriate methods for their analysis is required. While analytical methodologies have been developed concomitant with the use of additives, these do not fulfil the current needs, set by legislation and modern material development. In this sense, the comprehensive separation of additives, including their metabolites, from the polymer is a gap of technology. Drivers behind the need are regulatory issues (REACH) and the efforts towards a circular plastics economy, where the multiple reuse of plastics becomes a rule. As a consequence the quality of recycling technology has to be ensured, and, structure-property relationships for their products need to be mapped. While the questions in the case of Post Industrial Waste are still fairly straightforward, Post Consumer Waste significantly expands the range of analytical challenges. These are, for example, set by the presence of multiple additives in a compositionally non uniform polyolefin matrix. Furthermore, possible contaminations, brought in from the first life cycle, need to be tracked. A newly developed analytical approach will be presented, which in future can become part of the industrial routine portfolio and thus foster the transformation towards a circular plastics economy.
Advancements in Stabilization for Polyethylene in Rotational Molding
John Sigler, February 2020
Abstract As polyethylene production has increased and the rotational molding market has expanded, there is a growing demand for improved performance in thermal and ultraviolet light stabilization for end-use applications. These requirements, coupled with the current drivers towards sustainable and environmentally-friendly solutions, present opportunities for additives in polyethylene. In this presentation, we present solutions that enable players throughout the supply chain to produce products that enhance durability, reduce energy cost in production, increase throughput, and accommodate rework and recycle requirements.
Evaluation of High Performance Phosphite in PP and HDPE
Hayder Zahalka Hayder, February 2020
Wide range of sterically hindered phenols (primary antioxidants) are used in conjunction with organo-phosphites (secondary antioxidants) for adequate stabilization of Polypropylene and Polyethylene for meeting specific application requirements. These antioxidants inhibit polymer autoxidation throughout the value chain from manufacturing to end use applications and recycling. The guidelines for phosphite selection include % phosphorous, chemical structure, thermal stability, solubility in resin and efficacy. In this presentation we will focus on the quest for robust and high performance stabilization system (lower additive loadings, better color retention, resistance to gas fading etc) for Polypropylene and HDPE for meeting specific performance requirement.
Bio-based Antimicrobial Additive – Safety with Sustainability
Amrita Poyekar, February 2020
Polymers have become a significant part of our lives, owing to their extended range of applications. The possibilities to achieve more impressive functionalities makes this material promising for the future advancement. One of such application, which is gaining attention, is bacterial control properties imparted to plastics by using suitable additives. A suitable antimicrobial additive plays a crucial role in making plastics safer for us. Further, the presence of microbes may also negatively affect the aesthetics and properties of the product (such as mechanical, electrical and other properties). The bio-film formation may exhibit severe dust pick-up and may also impart foul odor in the plastic articles. The traditional solutions typically include metal-based compounds, nanoparticles, toxic element containing compounds or other categories, wherein the biocide properties can be attained. The trend of bio-based and safer additives poses the demand for more benign products. FinaGuard AM is well-suited for such requirements, as it is a unique naturally derived antibacterial additive, free from metal/nanoparticles offering excellent performance in Gram (-) & Gram (+) bacteria. It brings forth manifold benefits such as effective antimicrobial performance, sustainability as well as safety during handling & service life. FinaGuard AM is an internal additive, therefore, can be incorporated in plastics via a masterbatch route. It has been tested by JIS Z 2801: 2010 in polyolefins and PVC. The potential application spectrum for FinaGuard AM is evidently wide, for instance – medical apparatus, domestic products (e.g. kitchen utensils, flooring, bath mats, shower curtains), fabrics/clothing, furniture (e.g. chair handle, table tops, door handles) and construction materials/interiors (e.g. tiles, wallpaper, flooring).
Bioadditives: Renaissance and the Latest Scoop
Rudolf Pfaendner, February 2020
Most plastic additives are manufactured today from fossil resources through established chemical processes. Additives from natural resources (“Bioadditives”) are known as well and representatives of several additive classes have been used for many years. However, the need for bioadditives is increasing to replace traditional fossil based additives. Moreover the growth of biopolymers enforces the requests for natural based additives to offer fully biobased systems to the market and to support circular economy. Within the extensive variety of additives biobased products are found in the class of plasticizers, antioxidants, lubricants, antifogging agents and clarifiers. Plasticizers from different natural resources (citric acid esters, succinic acid esters, isosorbide esters) have captured a significant market share. Lubricants such as fatty acid esters and their salts are well-known standard products. On the other side several large additive areas such as flame retardants, light stabilizers or impact modifiers are still not represented. Phenolic structures are omnipresent in nature and can be isolated from many plants [1]. Vitamin E (“Tocopherol”) is the classical example of a naturally based antioxidant providing excellent processing stability to polyolefins [2]. However, secondary antioxidants such as phosphites are not found in nature. To benefit from the well-known synergism of primary and secondary antioxidants in polymer stabilization a natural based alternative to phosphites is mandatory. The presentation will give an overview on bioadditives for plastics and will show new stabilizer concepts fully based on natural resources.
New Advances in Polyolefin Modifiers (Paper)
Charles Olsen, February 2020
The most recent developments in grafting technology for polyolefins have been applied on an industrial scale to help solve challenges in performance and processing of these ubiquitous materials. Through the use of solid phase grafting, the unique properties of each polymer can be retained while reducing undesirable side reactions. This approach has been applied to a wide range of polyolefins to address key performance needs; specifically the creation of Polyolefin Alloys. These grafted side chains of LDPE / PS, LDPE / SAN, PP / SAN modify the properties of the bulk polymer. This paper will illustrate the resulting properties when incorporated into blends of other polyolefins, ABS, PLA, and PC blends. The use of solid phase grafting technology also allows for the facile addition of MAH to a range of polyolefin backbones. The effectiveness of the method results in polyolefins which retain a high MFI, a high percent of MAH functionality and low volatility / residual MAH levels. HDPE, PP, POE, EBA, LLDPE grafted with MAH have all been successfully prepared and tested. These novel graft polyolefins exhibit excellent performance in a wide range of thermoplastic compounds and composites. In addition, a new approach to incorporating low MW functional additives into the polyolefin melt has been developed. Porous granules which can adsorb up to 80% by weight are now available in a variety of polymers including LLDPE, PP and EVA. The porous polyolefin carrier absorbs the liquid additive and allows the resulting dry granule to be metered into the compound as with any other solid additive. The result is a much better match of melt viscosity with more thorough mixing and incorporation into the compound. A wide range of liquid additives and additive blends have been successfully incorporated into polyolefin compounds including; Crosslinking of PE through the Monosil process; Vinyl Silane / peroxide, Addition of Boron based HFFR, Addition of MAH, Silicone oils and gums Antistats, anti-fog, slip aides and other low MW additives.
New Advances in Polyolefin Modifiers (Presentation)
Charles Olsen, February 2020
The most recent developments in grafting technology for polyolefins have been applied on an industrial scale to help solve challenges in performance and processing of these ubiquitous materials. Through the use of solid phase grafting, the unique properties of each polymer can be retained while reducing undesirable side reactions. This approach has been applied to a wide range of polyolefins to address key performance needs; specifically the creation of Polyolefin Alloys. These grafted side chains of LDPE / PS, LDPE / SAN, PP / SAN modify the properties of the bulk polymer. This paper will illustrate the resulting properties when incorporated into blends of other polyolefins, ABS, PLA, and PC blends. The use of solid phase grafting technology also allows for the facile addition of MAH to a range of polyolefin backbones. The effectiveness of the method results in polyolefins which retain a high MFI, a high percent of MAH functionality and low volatility / residual MAH levels. HDPE, PP, POE, EBA, LLDPE grafted with MAH have all been successfully prepared and tested. These novel graft polyolefins exhibit excellent performance in a wide range of thermoplastic compounds and composites. In addition, a new approach to incorporating low MW functional additives into the polyolefin melt has been developed. Porous granules which can adsorb up to 80% by weight are now available in a variety of polymers including LLDPE, PP and EVA. The porous polyolefin carrier absorbs the liquid additive and allows the resulting dry granule to be metered into the compound as with any other solid additive. The result is a much better match of melt viscosity with more thorough mixing and incorporation into the compound. A wide range of liquid additives and additive blends have been successfully incorporated into polyolefin compounds including; Crosslinking of PE through the Monosil process; Vinyl Silane / peroxide, Addition of Boron based HFFR, Addition of MAH, Silicone oils and gums Antistats, anti-fog, slip aides and other low MW additives.
Building Sustainability into Additive R&D and Product Portfolios
Zach Adams, February 2020
Plastics are a major focus of sustainability efforts around the world, due to their ubiquity and the volume of waste they generate. Many companies are proactively applying environmental goals throughout the plastics lifecycle, from R&D through application development, manufacturing and disposal. While they may not produce plastics, additive manufacturers nonetheless are playing an important role in reducing environmental impacts and advancing environmental objectives. Examples include promoting the increased use of recycled plastic content by formulating additives such as performance modifiers specifically designed to optimize recycled content. Or by replacing or removing ingredients which could negatively affect recycling streams or cause concern with regards to migration or extraction. Further, additive manufacturers are addressing the challenge of excessive packaging by developing products that maintain desirable properties, such as barrier performance, while using thinner walls or film gauges. Used in food packaging, innovative additives can avoid the need for preservatives in the food itself to support the Clean Label trend, while extending shelf life to reduce waste. This paper will describe how Milliken is adding sustainability considerations to its goals for the research and development of additives for virgin and recycled resins, as well as expanding its portfolio with products specifically tailored to meeting environmental goals across the plastics lifecycle.
Polyolefin Recyclates Need Novel Stabilizer Systems
Rudolf Pfaendner, February 2020
Circular economy will change our way to design plastic products to provide greater durability, reuse and high-quality recycling. The European Union will considerably reduce landfill, introduce economic incentives to put greener products on the market and drive investments and innovation to circular solutions. In addition to improve design to make plastic products easier to recycle, collection and sorting will be expanded and viable markets for recycled and renewable plastics will be created [1]. Recycling of plastics will grow and the quality of recyclates has to be improved to replace pristine polymers. Additives such as stabilizers, repair additives, compatibilizers and odor neutralizing agents play an important role to enhance and to maintain the quality of recyclates [2]. Stabilizers for recyclates fulfil the same function as in virgin material namely to protect the polymer from oxidative degradation during processing and to maintain the properties during use. Consumed stabilizers of the first application have to be replaced at least and/or adjusted to the requirements of the second application. For example a recyclate from a short-time packaging application is not sufficiently stabilized for a long-term service life. Moreover, there are structural differences between virgin and recycled polymers. Recycled plastics show usually predamage through oxidation from the first service life e.g. an increased carbonyl and carboxyl group content versus virgin material is found in polyolefins. Moreover the oxidized molecular structures act as initiator sites and prodegradants accelerating recyclate degradation during processing and use [3, 4]. Furthermore, recycled plastics are often mixtures from different manufacturers and formulations with various additives and may contain more or less impurities. Specific recyclate stabilizers were developed in the past, however mainly as a variation of standard virgin stabilizer systems. Selected combinations of phenolic antioxidants, phosphites and antiacids in optimized ratio prove that the best cost/performance stabilizer combination for recyclates is different from the one for virgin material. Now a new generation of improved recyclate stabilizer systems combines antioxidants and selected alditols [5]. These systems may act in several ways: interaction with carbonyl groups, hydroperoxide decomposition and metal deactivation, thus addressing the potential weaknesses of recycled plastics. The newly developed stabilizer systems for polyolefins show excellent processing stability of PP and PE recyclates and outperform alternative stabilizers in long-term thermal stability. For commercialization of the technology an industrial partnership is established.
Mechanical Recycling - Rethinking the Additive Systems for Enhanced Recyclability
Yvonne Hed, February 2020
The global production of plastic reached 350 million tons in 2017, of which a large part ends up in landfill and/or incineration. Further, 1.5 to 4% of the global production of plastics ends up in marine littering every year and plastic stand for 80% of the marine littering (1). EU has set ambitious goals to reduce the littering from plastic packaging with an aim to recycle 50% plastic packaging by 2025 and 55% by 20302. Reaching these goals requires larges changes within the whole plastic industry (2) and new innovative solutions in mechanical recycling. Today, the stabilization additive packages are often not designed for recycling. When plastics are recycled the polymer will experience multiple processing steps which means polymer degradation unless actions are taken to secure enhanced stabilization. This talk will demonstrate the effect on polymer properties during four recycling steps without extra stabilization, and with multiple additions of antioxidants in the recycling process. The effects of the most used “traditional” antioxidants standing for the largest antioxidant consumption - AO1010, AO1076 and P168 - are demonstrated (3). The study demonstrates the effects on polymer properties in the two mentioned scenarios and identifies gaps-to-close related to use of traditional additives systems in mechanical recycling. For example, how much additives are needed to keep polymer properties intact in recycling and what unexpected properties are observed by accumulation of these additives and their by-products. 1 Jambeck et al. Plastic waste inputs from land into the ocean. Science (2015). 2 EuropeanCommission. A European strategy for plastics in a circular economy. 3 Maier, R. D. & Schiller, M. Handbuch Kunststoff-Additive. (2016).
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